EP1834369B1 - Batteries auto-assemblees de maniere electrochimique - Google Patents

Batteries auto-assemblees de maniere electrochimique Download PDF

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EP1834369B1
EP1834369B1 EP06717622.2A EP06717622A EP1834369B1 EP 1834369 B1 EP1834369 B1 EP 1834369B1 EP 06717622 A EP06717622 A EP 06717622A EP 1834369 B1 EP1834369 B1 EP 1834369B1
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metal
metal halide
group
positive electrode
cell
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EP1834369A4 (fr
EP1834369A2 (fr
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Glenn. G. AMATUCCI
Irene Plitz
Fadwa BADWAY
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Rutgers State University of New Jersey
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0422—Cells or battery with cylindrical casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/22—Immobilising of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0472—Vertically superposed cells with vertically disposed plates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/002—Inorganic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a new concept in the development of an electrochemically self assembled battery.
  • the self assembled chemistry relates to an ideal way to fabricate microbatteries.
  • microelectronic and microelectromechanical systems continues to decrease as a result of improved integration and microprocessing techniques.
  • the macroscopic power systems currently employed to power these microdevices are much larger than the devices themselves and require complex circuitry.
  • the search for micropower sources has recently raised an increasing amount of interest, the demand for suitable small-scale power system that meet microsystem power and energy requirements has yet to be fulfilled.
  • power supply miniaturization advanced to the microdevice scale would provide more control over the power delivery to each component of the microsystem and would also simplify electronic circuitry.
  • the incorporation of a micropower source directly into microsystems that also integrate communication and signalprocessing components would offer the advantage of complete autonomy, a critical feature in many applications such as microsensors. ( J. Long, B.
  • micro-power sources One crucial issue related to micro-power sources is to provide enough energy and power to all the components for the remote microsystem to function while minimizing the size of the power system. As constituent materials and fabrication techniques often restrict battery thickness, system optimization usually consists in minimizing footprint occupancy while meeting the energy and power requirements. This challenge opens opportunities for the development of fabrication technologies for materials in the micro and nano scale.
  • High-energy density primary and secondary batteries of relatively thin dimensions are currently commercially available.
  • These thick-film batteries are constructed with polymer electrolyte films laminated to the positive and negative electrodes and packaged with polylaminate aluminum/polyethylene heats sealable packaging material.
  • Major polymeric electrolytes W. H. Meyer, Adv. Mater., 10: 439 (1998 ), J.Y. Song, Y.Y. Wang and C.C. Wan, J. Power Sources, 77: 183 (1999 )
  • SPEs solid polymer electrolytes
  • the lithium battery technology consists of a negative electrode (Li metal), an electrolyte/separator (solid state lithium ion conductor) and positive electrode material. Successively deposited or self assembled architectures are very difficult to achieve in 3 dimensions and have poor prospects for robustness once assembled. The latter point is due to the tendency to form electronic shorts through the electrolyte/separator.
  • EP-A-0 149 421 discloses a solid electrolyte cell comprising an alkali metal anode (for example, of lithium), a halogen-containing organic polymer cathode and a solid electrolyte between the anode and the cathode.
  • the cathode comprises iodine-containing vacuum cyclised polyacrylonitrile and the solid electrolyte is preferably lithium iodide and halogen-free vacuum cyclised polyacrylonitrile.
  • the anode, cathode and solid electrolyte layers are formed separately and then assembled in a stack.
  • a halogen-free organic polymer coating may be provided on the surface of the anode that faces the cathode.
  • DE 39 30 804 A1 discloses a solid-state battery comprising an anode, a cathode and a solid electrolyte, in which the anode consists of a light metal coated with a charge transfer complex or a light metal charge transfer complex with an electron acceptor component.
  • the anode, cathode and solid electrolyte are formed separately and then assembled together in a stack.
  • US-A-4 007 122 discloses solid electrolytes for use in solid-state electrochemical devices.
  • the solid electrolytes include a lithium halide and a controlled amount of water to provide materials having adequate ionic conductivity and low electronic conductivity for use in solid state electrochemical devices such as electric cells, timers, capacitors, coulometers and rechargeable batteries.
  • the solid electrolyte may include a high surface area oxide, such as silica, alumina or mixtures of these.
  • the anode, cathode and solid electrolyte are formed separately and then assembled together in a stack.
  • the present invention provides a method for forming a single-layered electrochemical cell comprising a full tri-layer battery structure containing a discrete positive electrode, solid state electrolyte, and negative electrode formed in situ from self-assembled composites or nanocomposites.
  • a method for forming in situ an electrochemical cell structure consisting of positive electrode, solid state electrolyte and negative electrode from an ionically conducting composition comprising a metal halide composite comprising a metal cation and a halide anion is characterised by comprising:
  • the metal halide composite of the composition comprises a compound selected from the group consisting of an alkali metal halide, an alkaline earth metal halide, and a rare earth metal halide.
  • the alkali metal halide composite of the composition comprises an alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium.
  • the alkali metal halide composite of the composition comprises lithium iodide.
  • the alkaline earth metal halide composite of the composition comprises an alkaline earth metal selected from the group consisting of magnesium, calcium, strontium, and barium.
  • the rare earth metal halide composite of the composition comprises a rare earth metal selected from the group consisting of yttrium and lanthanum.
  • the metal halide composite of the composition comprises a halide selected from the group consisting of fluorine, bromine, iodine and chlorine.
  • the metal halide composite of the composition comprises a fluoride ion.
  • the metal halide composite of the composition comprises an iodide ion.
  • the forming step further comprises forming a compound comprising an oxidized iodate ion at the positive electrode upon application of a charging potential.
  • the forming step further comprises forming an oxidized compound comprising a polyiodide ion at the positive electrode upon application of a charging potential.
  • the fomring step further comprises forming an oxidized compound comprising a metal iodide at the positive electrode upon application of a charging potential.
  • the metal halide composite of the composition is a nanocomposite.
  • the metal halide composite further comprises an organic component.
  • the organic component is an organic material that forms compounds with iodine.
  • the organic material that forms compounds with iodine is poly(vinylpyrrolidone).
  • the organic component is a conductive compound.
  • the conductive compound is a compound selected from the group consisting of poly(2 vinylpyridine), polyethylene oxide, polyvinyldene fluoride, polythiophene, polyfluorothiophene, polypyrrole, polyaniline, and their respective monomers.
  • the ionically conducting composition further comprises a nanostructured inorganic component.
  • the nanostructured inorganic component is at least one compound selected from the group consisting of silicon oxide, aluminum oxide, barium titanate, and silicon nitride.
  • the metal halide composite of the composition further comprises at least one subgroup selected from the group consisting of water and hydroxyl ions.
  • the negative electrode further comprises a metal current collector.
  • the metal current collector of the negative electrode is formed of a metal selected from the group consisting of stainless steel, silicon, nickel, aluminum, tin, gold, silver, platinum, and copper.
  • the oxidized halide ion forms a complex with the metal current collector of the positive electrode.
  • the positive electrode comprises a metal current collector.
  • the metal current collector of the positive electrode is formed of a metal selected from the group consisting of stainless steel, copper, nickel, aluminum, gold, silver, and platinum.
  • the ionically conducting composition is deposited in a thickness of less than about 100 microns. According to another embodiment, the composition is deposited by a direct write technology.
  • the present invention enables the fabrication of small and/or complex three dimensional energy storage electrochemical cells.
  • compounds have been identified, which, when processed in the correct fashion, can be deposited or absorbed into a complex shape as a single layer material.
  • a voltage to this single layer material, a full tri-layer battery structure containing a discrete positive electrode, solid state electrolyte, and negative electrode is formed in-situ. This is a challenge and concept that has not been met or addressed to date.
  • the single layered cell enables the unparalleled capability to fabricate cells in three dimensions resulting in a very high energy density power source within very small and/or complex dimensions.
  • nanostructured metal fluorides can be converted to lithium fluoride and metal (See PCT/US2005/35625 , entitled “Bismuth Fluoride Based Nanocomposites as Electrode Materials” and U.S. Pat. Application No. 11/177,729 , entitled “Copper Fluoride Based nanocomposites as Electrode Materials; the contents of each of these applications is incorporated by reference herein).
  • This technology has enabled the reversible conversion reaction of these nanostructured metal fluorides for use as very high energy density electrodes for traditional lithium batteries.
  • that concept has been extended in reverse by starting the single layer battery with a nanostructured lithium halide and then applying charge.
  • such a cell is based on lithium metal anodes due to the intrinsic high voltage of lithium metal.
  • certain alkaline earth metals preferably magnesium or its alloys, may be utilized to enhance volumetric energy.
  • alkali metal halides, alkaline earth metal halides, or rare earth metal halides are used.
  • the iodides are most preferred, due to their high mobility, but bromides, chlorides, or fluorides may be utilized for the higher voltage they impart to the electrochemical cell.
  • lithium iodine chemistry is very difficult to short: when the two electrodes Li and I 2 are brought in contact, they form a LiI conversion product, which acts as a solid state electrolyte, thereby granting self healing attributes and immense robustness to the technology.
  • the cell reaction for the lithium iodine chemistry is: 2Li + I 2 ⁇ 2LiI
  • the cell is discharged and dead.
  • the focus of the present invention is to utilize a composite or nanocomposite form of the inactive discharge product LiI as the starting component and to reverse the reaction, demonstrated by the following simplistic representation: Lil ⁇ Li + I 2
  • the cell formed in-situ is similar to a simple Li-I 2 chemistry, it has a positive electrode which differentiates itself from such chemistries.
  • a highly ionically conductive, electrically insulative nanocomposite based on LiI and a binder is placed between two current collectors.
  • lithium ions Li +
  • the iodide anions I -
  • the lithium ions reduce and plate at the negative electrode in the form of lithium metal, thereby forming in-situ the lithium metal negative electrode.
  • the I - oxidizes either to form elemental iodine (I 2 ), polyiodides (I n ) form a complex with the metal current collector, such as Ni to form NiI 2 , or, even more preferably, the I - reacts with a complexing organic component, such as polyvinylpyrrolidone or conducting conjugated polymers such as poly(2-vinylpyridine), or other conjugated conducting polymers such as those based on thiophenes and anilines, and their respective monomers, which form a conducting composites with iodine.
  • a complexing organic component such as polyvinylpyrrolidone or conducting conjugated polymers such as poly(2-vinylpyridine), or other conjugated conducting polymers such as those based on thiophenes and anilines, and their respective monomers, which form a conducting composites with iodine.
  • the ionically conducting composition of the invention further comprises a nanostructured inorganic component.
  • the nanostructured inorganic component is at least one compound selected from the group consisting of silicon oxide, aluminum oxide, barium titanate, and silicon nitride or a mixture thereof.
  • a modified version of a high volumetric energy density rechargeable lithium / iodine cell is essentially formed in-situ.
  • the self assembled chemistry of the present invention allows unprecedented ease of fabricating thin cells in all three dimensions, which will enable exceptional utilization of valuable sensor surface area, easy tuning of the cell voltage by changing parallel vs. series configuration, high reliability, low cost, and easy hermetic sealing.
  • the present invention is used to power sensor and sensor arrays in an on-chip configuration where sensor electronics, communications and powering exist on a common platform.
  • incorporation of the power source directly on or in the substrate is vital to preserving small format.
  • Such on-chip incorporation will allow production of sensors in larger numbers for smart node array deployment that will be beneficial for applications such as infrastructure monitoring and in-vivo biomedical applications. Because it is desirable to preserve the surface area of the sensor, the fabrication of such power sources is focused in the third dimension or "z" direction.
  • the present invention is used to form three dimensional (3D) batteries.
  • Fig. 2 depicts a 3D cell fabricated according to the present invention where parallel plates of the battery are formed directly in the depth of the sensor substrate. This configuration enables the utilization of the silicon substrate in a multifunctional way.
  • the cell is fabricated by etching or ion milling parallel plates of a metal collector into the metal substrate. Parallel plates having a separation distance of approximately 25-50 microns are formed through micro wire EDM or laser micromachining. In other embodiments, the plates are micromilled to enable varying degrees of parallel and series connectivity.
  • the single layer nanocomposite composition of the present invention is deposited by direct write technology between the parallel plates followed by a top layer coating of a hermetic barrier based on inorganic or inorganic/organic hybrids containing an inorganic component including but not limited to aluminum oxides, metals, silicon oxides, titanium oxides, silicon nitrides, and the like.
  • the full cell then is fabricated by electrochemical polarization.
  • micromachining capabilities such as microwire electrodischarge machining (EDM) and laser micromachining can be used to form discrete 3 dimensional micro power cubes ("MPC"s) smaller than 1 mm in dimension.
  • EDM microwire electrodischarge machining
  • MPC micro power cubes
  • Example 1 Formation of electrochemical cells in situ from a nanocomposite of LiI and poly(vinylpyrrolidone) (PVP)
  • LiI and poly(vinylpyrrolidone) (PVP) were dissolved in methanol and dried in a glass Petri dish at 150°C under air. Afterwards, the material was ground and dried under vacuum. The resulting material was reground and placed inside of an electrochemical test cell of Swagelok construction. The cell was compressed such that the powder formed a densified disk of approximately 200 micron thickness. The cell was placed on a computer-controlled galvanostat and the cell was charged at a constant current of 10 ⁇ A.
  • the initial voltage of the cell was zero volts, consistent with the fact that only the LiI based composite but no electrochemical cell existed.
  • a long plateau develops at approximately 3.5V.
  • a 3-layer cell is formed in situ.
  • lithium metal is deposited at the negative current collector to form the anode and an iodine-PVP composite is formed by the oxidation of I - to an iodine species containing polyiodide.
  • the cell is placed on discharge to confirm the existence of the electrochemical couple.
  • a discharge plateau is developed during discharge between 2-2.5 V. This confirms the in-situ formation of a useable electrochemical cell and deliverance of useful electrochemical energy.
  • Example 2 Formation of electrochemical cells in situ from a nanocomposite of LiI and polyethylene oxide.
  • LiI and polyethylene oxide (PEO) were dissolved and cast in a solvent of acetonitrile.
  • the fabricated free-standing film was cut out and placed in an electrochemical cell and tested electrochemically as described in Example 1.
  • a temperature of 80°C was utilized to improve kinetics.
  • the cell showed no initial voltage.
  • a three layer cell was formed in-situ. The capacity of the cell could be recovered on subsequent discharges.
  • the length of the discharge corresponds directly with the length of the formation of the charge.
  • Table 1 summarizes the fabrication conditions and resulting electrochemical data of a number of examples of the present invention fabricated by mixing the indicated molecular percentage of organic compound, such as polyvinylpyrolidone (PVP), with acetone and a lithium iodide.
  • organic compound such as polyvinylpyrolidone (PVP)
  • PVP polyvinylpyrolidone
  • the solution was dried under indicated conditions and time. Afterwards the powder was transferred into a He filled glovebox of - 80°C dewpoint. The material was then characterized by Fast Fourier Transformed Infrared Spectroscopy (“FTIR”) and X-Ray Diffraction (“XRD”) for structural characteristics.
  • FTIR Fast Fourier Transformed Infrared Spectroscopy
  • XRD X-Ray Diffraction
  • ionic conductivity refers to the ability of a material to pass an electric current through the motion of electrically charged ions, in this case being Li + .
  • Table I Conditions and parameters for composite materials fabricated under a variety of conditions Sample number % PVP Anneal Temp, °C Anneal time, h Anneal Atm Acetone (g) Charge (c), Discharge (d), current/cycle (uA) Discharge time/cycle Conductivity (ms/cm) 1 10 130 3 air-ambient 5 c20, d5 54, 39, 18 2.40E-03 2 10 130 3 air-ambient 5 c40, d5 53, 37, 18, 14, 12 2.80E-03 3 10 130 3 air-ambient 5 c40, d5 62, 47, 55, 21, 15, 4 2.50E-03 4 10 130 6 air-ambient 5 c40, d5 26, 19 8.40E-04 5 10 130 air-ambient 5 c20, d5 171, 184, 79 2.60E-03 6 10 130 vac 5 c2.5, d2.5 23 1.60E-05 7 10 130 air-ambient 5 c2.5, d2.5 20, 40 1.08E-04 8 10 130 6 air
  • Fig. 7 is a bar graph summarizing the ionic conductivity of a number of the examples prepared as described in Example 3-as a function of synthesis.
  • the synthesis conditions are described on the Y axis.
  • dry indicates that LiI stored under anhydrous conditions in a glovebox was utilized as a precursor.
  • the ionic conductivities of the various LiI/PVP examples ranged from about 1 x 10 -1 mS/cm to about 9 x 10 -4 mS/cm; typically partially hydrated samples showed the best ionic conductivity under the conditions tested.
  • the charge-discharge curve in Fig. 8 shows the formation, first discharge curve and energy density calculations for Example 5 from Table 1.
  • the cell was initially partially charged to a current of 0.015 mA.
  • the initial voltage of the cell was zero volts, consistent with the fact that only the LiI composite but no electrochemical cell existed.
  • a long plateau develops at approximately 3.2V.
  • a 3-layer cell is formed in situ, resulting in a current of about 0.012 mA.
  • the cell was placed on discharge.
  • a discharge plateau between about 2.4-2.8 V developed.
  • the total discharge capacity of the cell was about 0.425 mAh.
  • discharge capacity As used herein, the terms “discharge capacity” and “specific capacity” are used interchangeably to refer to the amount of energy the LiI nanocomposite contains in milliamp hours (mAh) per unit weight. Based on a voltage of 2.6V, the total discharge energy was 1.105mWh or 3.99J. Upon recharge, the cell developed a long plateau at about 3.2 V, resulting in a current of about 0.012mA, confirming the electrochemical stability and reversibility of the cell comprising the LiI/10% PVP nanocomposite fabricated according to example 5. Based on a thickness of 0.1 mm and an area of 78 mm 2 , the energy density of the cell was calculated as about 0.51 J/mm 3 .
  • the charge-discharge curve in Fig. 9 shows the reformation, second discharge curve and energy density calculations for example 5 from table 1. It demonstrates that the capacity of the cell comprising the LiI/10% PVP nanocomposite fabricated according to example 5 is reversible.
  • the term "reversible discharge capacity" means that the LiI nanocomposite of the present invention may be recharged by passing a current through it in a direction opposite to that of discharge.
  • the cell was discharged at 184h.
  • the total discharge capacity of the cell was 0.460 mAh. Based on a voltage of 2.6V, the total discharge energy was 1.196 mWh or 4.31J.
  • the cell Upon recharge, the cell developed a long plateau at about 3V, resulting in a current of about 0.012mA, confirming the electrochemical stability and reversibility of the cell comprising the LiI/10% PVP nanocomposite fabricated according to example 5. Based on a thickness of 0.1 mm and an area of 78 mm 2 , the energy density of the cell after reformation and a second discharge was calculated as about 0.55 J/mm 3 . Therefore cell reformation followed the second discharge cycle and recharge.
  • the charge-discharge curve in Fig. 10 shows the formation, first discharge curve and-energy density calculations for 2 cells fabricated from composition of example 11 from table 1.
  • the cell was initially partially charged to a current of about 0.02 mA.
  • the initial voltage of the cell was zero volts, consistent with the fact that only the LiI composite but no electrochemical cell existed.
  • a long plateau develops at approximately 3.4V, corresponding to formation of a 3-layer cell in situ and a current of about 0.026 mA.
  • the cells were discharged; cells disassembled at this point clearly show metallic lithium on the negative electrode, indicating successful in-situ cell formation.
  • a discharge plateau between about 2.4-2.6 V developed during discharge.
  • the total discharge capacity of the cells was about 0.315 mAh. Based on a voltage of 2.6V, the total discharge energy was 0.819mWh or 2.95J.
  • the cells Upon recharge, the cells developed a long plateau at about 3.2 V, resulting in a current of about 0.026mA, confirming the electrochemical stability and reversibility of the cell comprising the LiI/10% PVP nanocomposite fabricated according to example 11. Based on a thickness of 0.1 mm and an area of 78 mm 2 , the energy density of the cells was calculated as about 0.38 J/mm 3 .
  • X-ray diffraction patterns of LiI nanocomposites of the present invention fabricated in the presence of different amounts of acetone show the formation of various useful composite phases comprising lithium and iodide, depending on the amount of acetone utilized in synthesis of the LiI nanocomposites. Since the X-rays are reflected by the atoms in each sample's lattice, and since the wavelength is of the same order of magnitude as interatomic distances in the solid state, the interference among the reflected X-rays leads to a unique diffraction pattern for each specific material. As shown in Fig.
  • the XRD pattern of a LiI nanocomposite synthesized in the presence of 4g acetone has four XRD peaks at about 21, 24, 27.5 and 32 deg 2 ⁇ .
  • the reflections at about 21, 24 and 32 deg 2 ⁇ correspond to the trihydrate, LiI.3H 2 O.
  • the XRD pattern of a LiI nanocomposite synthesized in the presence of 5.5g acetone has the three trihydrate peaks, the 21, 24 and 32 deg 2 ⁇ peaks, and a peak at about 20.5 and at about 29.5 deg 2 ⁇ .
  • the 20.5 and 29.5 peaks correspond to the monohydrate LiI.H 2 O.
  • the XRD pattern of a LiI nanocomposite synthesized in the presence of 7g acetone displayed prominent peaks at 20.5 and at 29.5 deg 2 ⁇ , corresponding to the monohydrate, and an additional peak at (036).
  • the XRD pattern of a LiI nanocomposite synthesized in the presence of 10g acetone displayed peaks at about 21, 27.5, 29.5, and at 36 deg 2 ⁇ , most of which is attributed to the monohydrate version of LiI.
  • the remaining peaks identified by a dotted line are believed to be attributed to the dihydrate of LiI,. Therefore degree of hydration of the LiI based nanocomposite and accordingly the resulting electrochemical properties can be controlled by the acetone content of the original mixture.
  • Fig. 12 shows XRD patterns of a composite and nanocomposite prepared in accordance with Table I for examples 7-12. While 5g acetone was used in the synthesis of each of these examples, they were subjected to different post-fabrication combinations of anneal time and temperature. With reference to the phases identified in Fig. 11 , Fig. 12 shows that the thermal treatment induces significant changes in the degree of hydration of the LiI based nanocomposite.
  • Fig. 13 shows an FTIR spectrum of a composition of the present invention from Table I Example 3. The sample was removed from the cell after cycling for 6 cycles. A broad band observed at 800cmi -1 in the FTIR spectrum (circled) indicates the presence of iodate (IO 3 ) - compounds, which are formed in-situ during the oxidation/formation process in addition to polyiodides as discussed below.
  • iodate (IO 3 ) - compounds which are formed in-situ during the oxidation/formation process in addition to polyiodides as discussed below.
  • Fig. 14 shows a Raman spectra made of a 100 micron pellet which was fabricated and cycled as described above. After cycling the cell was opened and the formed battery was analyzed by local Raman spectroscopy in two areas, one next to the positive current collector, the second further away from the positive current collector towards the negative current collector. Both spectra consisted of polyiodides, the latter a tri-iodide, the former a penta-iodide. The location of each is consistent with its respective oxidation of the iodide anion.
  • Example 4 addition of nanostructured inorganic materials to the lithium iodide composite
  • a lithium iodide - PVP based composite was fabricated as detailed in Example 3 with the addition of 5wt% of 20nm particle size fumed silicon oxide.
  • the composite was heat treated in a teflon container at 130°C.
  • the sample was removed, ground to a powder, pressed to a 100 micron thick pellet and reannealed at 150°C for 0.5h.
  • Resulting discharge at 0.005mA /cm 2 revealed discharge times of 98h and 78h at a voltage of 2.5V for cycles 1 and 3 respectively.
  • the representative voltage profile is shown in Fig. 15 .
  • the examples of the present invention as described are embodiments of a self assembled cell based on lithium and iodine and do not limit the scope of the present invention. These examples demonstrate the principle of an electrochemically self assembled solid state battery that is enabled through the use of an ion conductor composite or nanocomposite that conducts the metal cation and/or a halide anion. Any such self assembled cell can be developed from what has been described herein as long as these conditions are met and if the anion can be complexed or form a solid oxidized product at the positive electrode.
  • a skilled artisan would appreciate that other embodiments of the present invention include, but are not limited to, embodiments based on magnesium and iodine, lithium and bromine, calcium and fluorine, magnesium and bromine, and the like.

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Claims (28)

  1. Un procédé pour former in situ une structure de cellule électrochimique consistant en une électrode positive, un électrolyte à l'état solide et une électrode négative, à partir d'une composition conductrice par voie ionique comprenant un composite d'un halogénure métallique comprenant un cation métallique et un anion halogénure, le procédé étant caractérisé en ce qu'il comprend
    a) l'application d'un potentiel électrique à la composition conductrice par voie ionique comprenant le composite d'un halogénure métallique, en l'absence d'une cellule électrochimique préexistante,
    b) la formation in situ d'une cellule électrochimique comprenant une électrode négative comprenant une forme réduite d'un cation métallique et une électrode positive comprenant une forme oxydée d'un anion halogénure.
  2. Le procédé selon la revendication 1, dans lequel le composite d'halogénure métallique comprend un composé choisi dans le groupe constitué par les halogénures de métal alcalin, les halogénures de métal alcalino-terreux et les halogénures d'un métal des terres rares.
  3. Le procédé selon la revendication 2, dans lequel le composite d'halogénure de métal alcalin comprend un métal alcalin choisi dans le groupe constitué par le lithium, le sodium, le potassium, le rubidium et le césium.
  4. Le procédé selon la revendication 3, dans lequel le composite d'halogénure de métal alcalin comprend l'iodure de lithium.
  5. Le procédé selon la revendication 2, dans lequel le composite d'halogénure de métal alcalino-terreux, comprend un métal alcalino-terreux choisi dans le groupe constitué par le magnésium, le calcium, le strontium et le baryum.
  6. Le procédé selon la revendication 2, dans lequel le composite d'halogénure de métal alcalino-terreux comprend un métal des terres rares choisi dans le groupe constitué par l'yttrium et le lanthane.
  7. Le procédé selon la revendication 1, dans lequel le composite à base d'halogénure métallique comprend un halogénure choisi dans le groupe constitué par le fluor, le brome, l'iode et le chlore.
  8. Le procédé selon la revendication 1, dans lequel le composite à base d'halogénure métallique comprend un ion fluorure.
  9. Le procédé selon la revendication 1, dans lequel le composite à base d'halogénure métallique comprend un ion iodure.
  10. Le procédé selon la revendication 1, dans lequel l'étape de formation b) comprend en outre la formation d'un composé comprenant un ion iodate oxydé sur l'électrode positive lors de l'application d'un potentiel de charge.
  11. Le procédé selon la revendication 1, dans lequel l'étape de formation b) comprend en outre la formation d'un composé comprenant un ion polyiodure sur l'électrode positive lors de l'application d'un potentiel de charge.
  12. Le procédé selon la revendication 1, dans lequel l'étape de formation b) comprend en outre la formation d'un composé comprenant un iodure métallique sur l'électrode positive lors de l'application d'un potentiel de charge.
  13. Le procédé selon la revendication 1, dans lequel le composite à base d'halogénure métallique est un nanocomposite.
  14. Le procédé selon la revendication 1, dans lequel l'halogénure métallique composite comprend en outre un composant organique.
  15. Le procédé selon la revendication 14, dans lequel le composant organique est un matériau organique qui forme des composés avec de l'iode.
  16. Le procédé selon la revendication 15, dans lequel le matériau organique qui forme des composés avec de l'iode est la poly(vinylpyrrolidone).
  17. Le procédé selon la revendication 14, dans lequel le composant organique est un composé conducteur.
  18. Le procédé selon la revendication 17, dans laquelle le composé conducteur est un composé choisi dans le groupe constitué par la vinylpyridine, la poly(2vinylpyridine), l'oxyde d'éthylène, l'oxyde de polyéthylène, le fluorure de vinyldène, le fluorure de polyvinylidène, le thiophène, le polythiophène, le fluorothiophène, le polyfluorothiophène, le pyrrole, polypyrrole, l'aniline, et la polyaniline.
  19. Le procédé selon la revendication 1, dans lequel la composition conductrice par voie ionique comprend en outre un composant inorganique nanostructuré.
  20. Le procédé selon la revendication 19, dans lequel le composant inorganique nanostructuré est au moins un composé choisi dans le groupe constitué par l'oxyde de silicium, l'oxyde d'aluminium, le titanate de baryum et le nitrure de silicium.
  21. Le procédé selon la revendication 1, dans lequel le composite d'halogénure métallique comprend en outre au moins un sous-groupe choisi parmi le groupe constitué par l'eau et les ions hydroxyles.
  22. Le procédé selon la revendication 1, dans lequel l'électrode négative comprend en outre un collecteur de courant en métal.
  23. Le procédé selon la revendication 22, dans lequel le collecteur de courant métallique de l'électrode négative est formé d'un métal choisi dans le groupe constitué par l'acier inoxydable, le silicium, le nickel, l'aluminium, l'étain, l'or, l'argent, le platine et le cuivre.
  24. Le procédé selon la revendication 1, dans lequel l'électrode positive est adjacente à un collecteur de courant en métal.
  25. Le procédé selon la revendication 22, dans lequel l'ion halogénure oxydé forme un complexe avec le collecteur de courant métallique de l'électrode positive.
  26. Le procédé selon la revendication 25, dans lequel le collecteur de courant métallique de l'électrode positive est formé d'un métal choisi dans le groupe constitué par l'acier inoxydable, le cuivre, le nickel, l'aluminium, l'or, l'argent et le platine.
  27. Le procédé selon la revendication 1, dans lequel la composition est déposée en une épaisseur inférieure à environ 100 microns.
  28. Le procédé selon la revendication 1, dans lequel la composition conductrice par voie ionique est déposée par une technique d'écriture directe.
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AU2006206816B8 (en) 2011-03-10
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JP5443690B2 (ja) 2014-03-19
US9331357B2 (en) 2016-05-03
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WO2006078472A3 (fr) 2006-12-21
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KR20070107010A (ko) 2007-11-06
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US20090004560A1 (en) 2009-01-01
WO2006078472A2 (fr) 2006-07-27

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